Determination of Solution Polymerization Kinetics by Near-Infrared Spectroscopy. 1. Living Anionic Polymerization Processes

Timothy Edward Long, H. Y. Liu, B. A. Schell, D. M. Teegarden, D. S. Uerz

Research output: Contribution to journalArticle

65 Citations (Scopus)

Abstract

Near-infrared (NIR) spectroscopy (1.0–2.5 µm or 10 000–4000 cm−1) was successfully utilized to monitor monomer conversion during conventional, anionic solution polymerization. The conversion of the vinyl protons in the monomer to methylene protons in the polymer was easily monitored under conventional (10–20% solids) solution polymerization conditions. Despite the presence of the NIR probe, the “living” nature of the polymerizations was maintained in all cases. Both styrene and isoprene polymerization kinetics were investigated in nonpolar and polar solvents, and relative rate constants were compared to values previously reported in the literature. In addition to the need for an inert probe, high sampling frequencies were required since polymerization times ranged from 5 s in tetrahydrofuran to 20 min in cyclohexane. Copolymerization kinetics have also been studied in order to determine the feasibility of NIR as an on-line structural probe. In fact, preliminary data indicate that NIR is capable of detecting sequence distributions for tapered block copolymers, geometric isomer content, and reactivity ratios for free-radical copolymerization. Future studies will focus on the application of NIR to elucidate polymerization mechanisms and deleterious side reactions.

Original languageEnglish
Pages (from-to)6237-6242
Number of pages6
JournalMacromolecules
Volume26
Issue number23
DOIs
Publication statusPublished - 1993 Jan 1
Externally publishedYes

Fingerprint

Living polymerization
Anionic polymerization
Near infrared spectroscopy
Polymerization
Kinetics
Infrared radiation
Copolymerization
Protons
Monomers
Isoprene
Styrene
Cyclohexane
Free radicals
Isomers
Block copolymers
Free Radicals
Solid solutions
Rate constants
Polymers
Sampling

ASJC Scopus subject areas

  • Organic Chemistry
  • Polymers and Plastics
  • Inorganic Chemistry
  • Materials Chemistry

Cite this

Determination of Solution Polymerization Kinetics by Near-Infrared Spectroscopy. 1. Living Anionic Polymerization Processes. / Long, Timothy Edward; Liu, H. Y.; Schell, B. A.; Teegarden, D. M.; Uerz, D. S.

In: Macromolecules, Vol. 26, No. 23, 01.01.1993, p. 6237-6242.

Research output: Contribution to journalArticle

Long, Timothy Edward ; Liu, H. Y. ; Schell, B. A. ; Teegarden, D. M. ; Uerz, D. S. / Determination of Solution Polymerization Kinetics by Near-Infrared Spectroscopy. 1. Living Anionic Polymerization Processes. In: Macromolecules. 1993 ; Vol. 26, No. 23. pp. 6237-6242.
@article{28a8f72883bb45f789ad41272ffa72b2,
title = "Determination of Solution Polymerization Kinetics by Near-Infrared Spectroscopy. 1. Living Anionic Polymerization Processes",
abstract = "Near-infrared (NIR) spectroscopy (1.0–2.5 µm or 10 000–4000 cm−1) was successfully utilized to monitor monomer conversion during conventional, anionic solution polymerization. The conversion of the vinyl protons in the monomer to methylene protons in the polymer was easily monitored under conventional (10–20{\%} solids) solution polymerization conditions. Despite the presence of the NIR probe, the “living” nature of the polymerizations was maintained in all cases. Both styrene and isoprene polymerization kinetics were investigated in nonpolar and polar solvents, and relative rate constants were compared to values previously reported in the literature. In addition to the need for an inert probe, high sampling frequencies were required since polymerization times ranged from 5 s in tetrahydrofuran to 20 min in cyclohexane. Copolymerization kinetics have also been studied in order to determine the feasibility of NIR as an on-line structural probe. In fact, preliminary data indicate that NIR is capable of detecting sequence distributions for tapered block copolymers, geometric isomer content, and reactivity ratios for free-radical copolymerization. Future studies will focus on the application of NIR to elucidate polymerization mechanisms and deleterious side reactions.",
author = "Long, {Timothy Edward} and Liu, {H. Y.} and Schell, {B. A.} and Teegarden, {D. M.} and Uerz, {D. S.}",
year = "1993",
month = "1",
day = "1",
doi = "10.1021/ma00075a018",
language = "English",
volume = "26",
pages = "6237--6242",
journal = "Macromolecules",
issn = "0024-9297",
publisher = "American Chemical Society",
number = "23",

}

TY - JOUR

T1 - Determination of Solution Polymerization Kinetics by Near-Infrared Spectroscopy. 1. Living Anionic Polymerization Processes

AU - Long, Timothy Edward

AU - Liu, H. Y.

AU - Schell, B. A.

AU - Teegarden, D. M.

AU - Uerz, D. S.

PY - 1993/1/1

Y1 - 1993/1/1

N2 - Near-infrared (NIR) spectroscopy (1.0–2.5 µm or 10 000–4000 cm−1) was successfully utilized to monitor monomer conversion during conventional, anionic solution polymerization. The conversion of the vinyl protons in the monomer to methylene protons in the polymer was easily monitored under conventional (10–20% solids) solution polymerization conditions. Despite the presence of the NIR probe, the “living” nature of the polymerizations was maintained in all cases. Both styrene and isoprene polymerization kinetics were investigated in nonpolar and polar solvents, and relative rate constants were compared to values previously reported in the literature. In addition to the need for an inert probe, high sampling frequencies were required since polymerization times ranged from 5 s in tetrahydrofuran to 20 min in cyclohexane. Copolymerization kinetics have also been studied in order to determine the feasibility of NIR as an on-line structural probe. In fact, preliminary data indicate that NIR is capable of detecting sequence distributions for tapered block copolymers, geometric isomer content, and reactivity ratios for free-radical copolymerization. Future studies will focus on the application of NIR to elucidate polymerization mechanisms and deleterious side reactions.

AB - Near-infrared (NIR) spectroscopy (1.0–2.5 µm or 10 000–4000 cm−1) was successfully utilized to monitor monomer conversion during conventional, anionic solution polymerization. The conversion of the vinyl protons in the monomer to methylene protons in the polymer was easily monitored under conventional (10–20% solids) solution polymerization conditions. Despite the presence of the NIR probe, the “living” nature of the polymerizations was maintained in all cases. Both styrene and isoprene polymerization kinetics were investigated in nonpolar and polar solvents, and relative rate constants were compared to values previously reported in the literature. In addition to the need for an inert probe, high sampling frequencies were required since polymerization times ranged from 5 s in tetrahydrofuran to 20 min in cyclohexane. Copolymerization kinetics have also been studied in order to determine the feasibility of NIR as an on-line structural probe. In fact, preliminary data indicate that NIR is capable of detecting sequence distributions for tapered block copolymers, geometric isomer content, and reactivity ratios for free-radical copolymerization. Future studies will focus on the application of NIR to elucidate polymerization mechanisms and deleterious side reactions.

UR - http://www.scopus.com/inward/record.url?scp=0027912431&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0027912431&partnerID=8YFLogxK

U2 - 10.1021/ma00075a018

DO - 10.1021/ma00075a018

M3 - Article

AN - SCOPUS:0027912431

VL - 26

SP - 6237

EP - 6242

JO - Macromolecules

JF - Macromolecules

SN - 0024-9297

IS - 23

ER -